WO1995005407A1 - Cross-linkable oligomers or polymers - Google Patents
Cross-linkable oligomers or polymers Download PDFInfo
- Publication number
- WO1995005407A1 WO1995005407A1 PCT/EP1994/002490 EP9402490W WO9505407A1 WO 1995005407 A1 WO1995005407 A1 WO 1995005407A1 EP 9402490 W EP9402490 W EP 9402490W WO 9505407 A1 WO9505407 A1 WO 9505407A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oligomers
- polymers
- group
- crosslinkable
- vinyl
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3833—Polymers with mesogenic groups in the side chain
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/40—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals
- C09K19/406—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals containing silicon
- C09K19/408—Polysiloxanes
Definitions
- the invention relates to crosslinkable, ferroelectric or • antiferroelectric, liquid crystalline properties having oligomers or polymers characterized by a main chain, at least one crosslinkable side group and at least one side chain with a chiral group.
- Broer et al. describe the production of liquid-crystalline networks with smectic, cholesteric or nematic liquid-crystalline behavior. They start from low molecular weight liquid-crystalline precursors which carry no, one or two polymerizable units. A photopolymerization process within the liquid-crystalline phase gives them a network in which the properties of the LC material are fixed. In this way it is possible to produce layers for selective reflectors for electromagnetic radiation, to manufacture polymer-dispersed displays and, not least, to manufacture piezoelectric materials.
- Finkelmann et al. describe the production of highly oriented LC networks from weakly pre-crosslinked polymers, which are oriented by mechanical forces and then fixed in this orientation by a further crosslinking step.
- the materials produced in this way essentially have smectic, nematic and cholesteric-liquid-crystalline phases.
- RAM Hikmet describes the production of a polar ordered ferroelectric network. This network is created in the same way as by Broer et al. described. Starting from a low molecular weight mixture of LC materials, some of which contain polymerizable groups, a photopolymerization process in the chiral, polar ordered ferroelectric liquid crystalline Phase creates a network. This network has piezoelectric properties.
- X is a direct bond, 0, 0C0, C00 or -C ⁇ H ⁇ O- and the symbols
- Y are independently a direct bond, 0, 0C0 or C00.
- radicals K correspond in particular to the formulas
- the spacers are usually linked to K via ester or ether groups or a direct bond.
- the spas usually contain 2 to 30, preferably 2 to
- Alkyl radicals R are, for example, C 1 -C 3 -alkyl, preferably C 1 -C -alkyl, it being assumed that the radicals R should be shorter-chain than the spacers.
- the radicals R can be branched, but preferably linear; they correspond, for example, to the formulas:
- the known mesogenic groups can in turn be used as residues M.
- Aromatic or heteroaromatic groups containing radicals are particularly suitable.
- the mesogenic residues correspond in particular to the formula III
- r are 1 to 3.
- R is preferably 1 or 2.
- radicals A are generally aromatic carbocyclic or heterocyclic ring systems which are optionally substituted by fluorine, chlorine, bromine, cyano, hydroxyl or nitro and which correspond, for example, to the following basic structures:
- mesogenic groups M are e.g.
- Chiral groups F have at least one asymmetric carbon atom.
- R 1 is a Ci- to C ⁇ 2 alkyl, which can be chiral or achiral.
- Preferred radicals R 1 are, for example:
- CH 3 CH 3 CH 3 CH 3 CH 3 n 1 to 12.
- Networkable groups F correspond in particular to the formulas
- F is a polymerizable radical and the spacer is defined as indicated.
- Polymerizable radicals F are, for example:
- oligomers and polymers according to the invention are synthesized by methods generally described in the literature.
- an acrylate capable of crosslinking is then possible in two stages.
- a polymerizable acrylate which carries a chiral side chain can be copolymerized with a further polymerizable acrylate which still allows the introduction of a polymerizable group.
- a polymerizable acrylate which carries a chiral side chain can be copolymerized with a further polymerizable acrylate which still allows the introduction of a polymerizable group.
- the functionalizable group which allows the introduction of a polymerizable group, is usually a COO or OH group which can be prepared by conventional methods, e.g. Esterification reactions in the presence of dicyclohexylcarbodiimide (DCC), can be reacted with polymerizable units.
- DCC dicyclohexylcarbodiimide
- Crosslinkable siloxanes are produced analogously to the production of liquid-crystalline side chain siloxanes (cf., for example, Poths et al. Adv. Mat. 4, (1992), 351).
- a mesogenic precursor which on the one hand can be further functionalized and on the other hand carries a terminal vinyl group, is bound to the hydrosiloxane by insertion into the SiH bond.
- the chiral and polymerizable groups are bound to the functional position of the mesogenic precursor, optionally in one reaction step, for example by DCC esterification.
- the connections according to the invention are preferably suitable for use in flexible electro-optical display elements as well as in pyro- or piezoelectric arrangements.
- transition temperatures were determined by polarization microscopy (Olympus BH 2 in conjunction with Mettler heating system FP90 / 82) and by means of DSC (Perkin Elmer DSC 7).
- the liquid-crystalline prepolymer is dissolved in 10 ml of methylene chloride and 2% by weight of a photoinitiator (for example 2,2-dimethoxy-2-phenylacetophenone) is added. The solvent is then removed in a high vacuum. The resulting mixture of prepolymer and photoinitiator is then poured into a glass cell provided with a conductive, transparent layer and additionally containing an orientation layer with a clear space of 4 ⁇ m in the molten state. Orientation takes place by slow cooling from the isotropic phase under an applied electric field. The orientation can be improved if several temperature cycles in the range between 30 ° C and 60 ° C are carried out with an applied electric field (5 Hz, 400 Vpp).
- a photoinitiator for example 2,2-dimethoxy-2-phenylacetophenone
- the ferroelectric switching of the sample can be observed directly during this procedure.
- the spontaneous polarization at 40 ° C is approx. 55 nC / cm 2 .
- the switching time has a value of 35 ms.
- the photopolymerization of the sample is then carried out in such a way that a DC voltage of 200 V is applied and, with an electrical field applied, the sample is exposed at a temperature of 40 ° C. for 1.5 h with a Spectronics ENF 260-C lamp at 365 nm.
- the lamp output was approx. 6W, the distance to the sample was approx. 2 cm.
- a sinusoidal (30 Hz) force F (peak O-10N) is applied to the cell in the direction of the cell normal by means of a piezotranslator ("force transmitter") from Physik Instrumente, type P-910.414, which is applied by means of a load cell, type 9203 , and a charge amplifier, type 5011 (both from Kistler) is measured.
- the charges Q induced sinusoidally in the material are measured on the electrodes by means of a type 5011 charge amplifier (from Kistler).
- a piezoelectric coefficient of d 33 4 pC / N was measured for the cell according to Example 4 at room temperature. The piezo effect is stable even after heating to 55 ° C and cooling again.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP94924294A EP0713499B1 (en) | 1993-08-14 | 1994-07-28 | Cross-linkable oligomers or polymers having ferroelectric or anti-ferroelectric liquid crystal properties |
DE59405323T DE59405323D1 (en) | 1993-08-14 | 1994-07-28 | CROSSLINKABLE OLIGOMERS OR POLYMERS WITH LIQUID CRYSTALINE FERROELECTRIC OR ANTI-FERROELECTRICAL PROPERTIES |
JP7506703A JPH09504309A (en) | 1993-08-14 | 1994-07-28 | Crosslinkable oligomer or polymer |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4327359.9 | 1993-08-14 | ||
DE4327359A DE4327359A1 (en) | 1993-08-14 | 1993-08-14 | Crosslinkable oligomers or polymers |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995005407A1 true WO1995005407A1 (en) | 1995-02-23 |
Family
ID=6495205
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1994/002490 WO1995005407A1 (en) | 1993-08-14 | 1994-07-28 | Cross-linkable oligomers or polymers |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0713499B1 (en) |
JP (1) | JPH09504309A (en) |
DE (2) | DE4327359A1 (en) |
WO (1) | WO1995005407A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19750628A1 (en) * | 1997-11-14 | 1999-05-20 | Heino Prof Dr Finkelmann | Preparation of a liquid crystal hydrogel |
DE19857691A1 (en) * | 1998-12-14 | 2000-06-15 | Consortium Elektrochem Ind | Liquid crystalline organosiloxane, useful for the production of pigments and optical elements is cross-linkable to form a three dimensional network. |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0291427A1 (en) * | 1987-05-13 | 1988-11-17 | Rhone-Poulenc Chimie | Liquid-crystal polymers with mesogen side groups, made from ethylenically unsaturated polymers, and process for making them |
WO1992001764A1 (en) * | 1990-07-20 | 1992-02-06 | Hoechst Aktiengesellschaft | Si-CONTAINING, FERROELECTRIC LIQUID CRYSTAL COPOLYMERS, A PROCESS FOR PRODUCING THE SAME, MIXTURES OF THESE COPOLYMERS WITH LOW MOLECULAR WEIGHT LIQUID CRYSTALS AND THEIR USE IN ELECTRO-OPTIC COMPONENTS |
EP0548808A2 (en) * | 1991-12-20 | 1993-06-30 | Idemitsu Kosan Company Limited | High polymer and ferroelectric liquid crystal composition utilizing same |
-
1993
- 1993-08-14 DE DE4327359A patent/DE4327359A1/en not_active Withdrawn
-
1994
- 1994-07-28 WO PCT/EP1994/002490 patent/WO1995005407A1/en not_active Application Discontinuation
- 1994-07-28 EP EP94924294A patent/EP0713499B1/en not_active Revoked
- 1994-07-28 DE DE59405323T patent/DE59405323D1/en not_active Expired - Lifetime
- 1994-07-28 JP JP7506703A patent/JPH09504309A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0291427A1 (en) * | 1987-05-13 | 1988-11-17 | Rhone-Poulenc Chimie | Liquid-crystal polymers with mesogen side groups, made from ethylenically unsaturated polymers, and process for making them |
WO1992001764A1 (en) * | 1990-07-20 | 1992-02-06 | Hoechst Aktiengesellschaft | Si-CONTAINING, FERROELECTRIC LIQUID CRYSTAL COPOLYMERS, A PROCESS FOR PRODUCING THE SAME, MIXTURES OF THESE COPOLYMERS WITH LOW MOLECULAR WEIGHT LIQUID CRYSTALS AND THEIR USE IN ELECTRO-OPTIC COMPONENTS |
EP0548808A2 (en) * | 1991-12-20 | 1993-06-30 | Idemitsu Kosan Company Limited | High polymer and ferroelectric liquid crystal composition utilizing same |
Also Published As
Publication number | Publication date |
---|---|
DE4327359A1 (en) | 1995-02-16 |
EP0713499A1 (en) | 1996-05-29 |
DE59405323D1 (en) | 1998-04-02 |
JPH09504309A (en) | 1997-04-28 |
EP0713499B1 (en) | 1998-02-25 |
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